Conversion of hydrocarbon oils into gasoline



Nov. 12, 1940. R. F. RUTHRUFF CONVERSION OF HYDROCARBON OILS INTO GASOLINE 2 Sheets-Sheet l original Filed Dc. 17, 1934 Gttomeg -NOL 12,1940.` R, P RUTHRUFF 2,221,425

CONVERSION OF HYDROCABON OILS INTO GASOLI-NE Original Filed Dec. 17, 1934 2 Sheets-Sheet 2 sra/L/zm 'Finished maentor Rob ert FRI/#Muff liy y Fig Patented Nov. l2, 1940 UNITED STATES 2,221,425 CONVERSION or HYDnocARBoN oILs INT GAsouNE Robert F. Ruthruff, Nutley, Ni J., assignor to 4Standard Oil Company, Chicago, Ill., a corporation of Indiana Griginal application December 17, 1934, Serial No. 757,902. Divided and this application February 2, 1939, Serial No. 254,

7 Claims.

This invention relates to an improvement inthe conversion of heavy oils into gasoline, More speciiically, it relates to an improved combinationv of an oil cracking unit, preferably a complete unit of the type which utilizes crude oil as charging stock and eliminates gasoline and heavy fuel oil as its principal liquid products, together with one or two gas polymerization units functioning. to

convert the gas from the crackingilunit to additional liquid products.

Briey described, myimproved process is characterized by the fact that I take the gas streams from the cracking section of the oil cracking unit and subject them to polymerization, returning the l5 liquid products from thev polymerization section to the cracking system. The gas streams from the cracking section, preferably after elimination of methane and hydrogen, are preferablyseparated into two fractions, one of which contains ethylene as a predominating unsaturated constituent, the other fraction containingpropylene-butylene as its predominating unsat` urated constituents. I preferably subject the latter fraction to catalytic polymerization at relatively low temperatures and pressures and the former 'fraction to non-catalytic polymerization at relatively high temperatures and pressures.

l'. prefer to combine thetotal liquid products, i. e.

gasoline and heavier, from both polymerization systems and return them to the cracking system whereby polymerization products heavier than gasoline are subjected to cracking and polymerized products of gasoline boiling range are eliminated from the system in admixture with the cracked gasoline.

Unconverted gases lfrom the polymerization section or sections may be eliminated from the sys, tem or may be recovered and subjected to a high temperature gas cracking step in order to gen- .;3 erate additional unsaturated gases which .may be returned to, r,the polymerization section or sections. In case I operate such a gas cracking step, the unconverted gases from the polymerization section or sections will ordinarily .be fractionated and recovered in conjunction with the saturated gases from the crude oil which are recovered by fractionation of the light virgin gasoline from the crude oil.

By means of my improved combination process considerable increases in the yield and quality of the total gasoline obtained from the crude'oil are realized. Since ethylene is not readily converted by improved catalysts which rapidly andsnioothly convert higher gaseous oleiins to liquids, my combination of high pressure polymerization and catalytic polymerization with the oil cracking system leads to optimum results. Furthermore, by the catalytic polymerization step' I may eliminate all, or essentially all, of butylene and iso-butylene from the cracked gasoline produced by the system. Since butylene and iso-butylene have a higher vapor pressure than butane and iso-butane this permits increasing the butane content of the gasoline whereby its volatility and starting qualities may be improved without encountering difliculties from excess uncontrolled volatility as reected in practice by tendency to vapor-lock automotive engines. The mixed polymerized and cracked gasoline produced by my system also usu- -ally has improved anti-knock value as compared to ordinary cracked gasoline. I also clay treat the vapors from the gasoline from the cracking unit and I have found that advantages in operation are obtained by clay treating the cracked gasoline vapors in admixture with vapors of polymerized gasoline.

The operation of my process Will be understood from the following detailed description and .reference to the drawings attached hereto and which form part of this specication, Figure 1 and Figure 2 taken together representing a diagrammatic elevational view of apparatus suitable for carrying out my process, Figure 1 representing the oil cracking section of the system while Figure 2 represents the gas polymerizing and gas cracking sections ofthe system.

The oil cracking system of my process may be varied in accordance with the type of crude handled and the other requirements of the particular situation. An arrangement which I ordinarily prefer is as follows:

Referring rst to Figure 1, cold crude oil is introduced through line I0 and preferably `is preheated by passing through reflux exchanger or coils I I in the upper section I2 of the crude flash tower, then through reux exchanger coils I3 in bubble tower I4, then through line I5 and heat exchanger I6 wherein additional heat ls picked V*up from the bottoms from bubble tower I 4, then through line II into upper section I 2 of the crude flash tower. In this section I2 of the tower light virgin naphtha plus all of the gases present in the crude are flashed off and are removed through line I'Ia. The unvaporized material is withdrawn ,from the\bottom of section I2 through line I8, and passes to a low point in the middle section I9 of the flash'tower, Where vapors of virgin heavy naphtha are ashed 01T and are withdrawn from the upper part of section I9 through line 20.v The drawn from the lower, part of section I9 through line 2l and introduced by pump 22 into :an elevated point in evaporator tower 23. Vapors of thus providing additional heat for stripping heavy naphtha from the crude oil in section I9 and being themselves condensed and withdrawn through line 2|. W.

In the evaporator 23 the gas' oil'and similar constituents of the crude oil are vaporized and the heavy residual portion of the crude is with drawn froml trap-out tray 26 by line 21 and goes to the so-called lviscosity breaker accumulator drum 28 from which it is pumped by pump 29 through viscosity breaker furnace 36 wherein *it is heated to peratures of 850 to 925 F. while und r press ys of 100 to750 lbs. per. sq. in. Appre iable conversion of heavy oils to gasoline takes place in the viscosity breaker furnace, ordinarily! about 5 to 15% of the heavy residue being con-- verted to gasoline. Another important. function of this furnace, however. is to viscosity break the heavy residue, i. e. to reduce its viscosity by moderate cracking. A11 products from the viscosity breaker furnace 30 pass through line 3| back to the lower section of the evaporator -23 bel low trap-out tray 26.

Vapors leavingthe evaporator through line 32 include all gasolineformed in the cracking system, together with all gas -oil, and are introduced through line 32 into the middle section of bubble tower I4. Qnconverted gas oil from the cracking;A furnaces, together-With fresh gas oil distilled in evaporator 23 from the crude residuum charged to' the evaporator 23 throughline 2|, are condensed in -bubble tower I4 and are withdrawn from the tower through line 33 and preferably through heat exchanger I6 to gas oil accumulator drum 34 from which the gas oilis pumped by pump 35, through linev36, to the gas oil furnace 31. In furnace 31 the gas oil issubjected to .cracking under relatively severe conditions,

c i.v e., temperatures of 900.1050 F. while under '1 and introduced into a low point of evaporator 23 pressure of 100-'750 lbs. per sq.;in. or more, the

rate of flow being such that a conversion of about 15% to 40% of the gas oil to gasoline is realizedI in one passage through the furnace. Products from the gas oil furnace 31 are withdrawn through line 38 and ordinarily are passed through valve 38 to -unheated reactio'nfdrum 40 wherein additional time for the cracking reactions is aiforded. Products leave the :reaction drumthrough valve 4I and line 42,- being intro-- duced into a low point in evaporator 23 below trap-out tray 26. I may, however, eliminate reaction'drum 48 by closing valves 39 and 4I and opening valves 43 and 44 in by-pass 45.

The heavy virgin naphtha vaporized from the crude oil in section I9v of the flash tower and withdrawn thrdu'gh une. 2c, 1s condensed by cooler 46 and passes to naphtha accumulatord'rum 41 from which it is withdrawn and pumped by pump '48 through line 48a to naphtha reformer furnace 49 wherein it is subjected to cracking at temperatures of 950 to 1100 F. while under pressures of 200 to 1500 lbs. per sq. in. to the end that the principal products are gasoline and gas andthe antiknockvalue of the virgin naphtha is materially increased. f The products are withdrawn from furnace 49 through line 50 'below trap-'out tray 26.. l

All of the gasoline formed in the three crackand trapped 'light ends. c

ing furnaces and most of the gas oil are vaporized to the bubble tower I4 but some of the heavy gas oil may be condensed in the evaporator 23 viscosity breaker furnace 30. The unvaporized cracked residuum or tar plus some unvaporized heavy gas oil are withdrawn from the bottom of evaporator 2 3 .through line 5I and valve 52 and pass to the bottom section 24 of the fuel oil flash tower which operates substantially at atmospheric pressure. In this section all remaining gas oil is flash distilled from the crackedl products as previously described, and heavy residual fuel oil is withdrawn from the system through line 53. I v A Cracked gasoline vapors and gasA are removed from the top of bubble tower I4 through line 54 and pass preferably through valve 55 into clay towers 56 and 51 wherein undesirable gum form- 20 ing constituents in the gasoline are polymerlzed andremoved in liquid form through valves 58A and 59, these liquid polymers being returned by pump 60 in line 6I to the evaporator 23 or to some other convenient point in the cracking system whereby these liquid polymers are recracked to gasoline. The clay treating towers may be eliminated from the system by closing inlet valve 55 and valve 62 in exit line 63 and opening valves 64 and 65, in by-pass 66. r

The gasoline'vapors in line 63 pass through condenser and cooler 61 which may be a water cooled condenser pure and simple or may combine 'cooling by heat interchange (with cooler streams in the cracking system) followed by water cooling. The condensed cracked products, together with any uncondensed gases, pass from condenser 61 through line 63 to separator 68 without any reduction in pressure, uncondensed gases being withdrawn, from separator 68 through/)oiftake 63, said gases consisting pre- 'dominatingly of hydrogen and 'methane The liquid condensates are removed from separator 68 and passed by pump 10 through line 1I to stabilizer 12 which is provided with suitable bottom heating means 13 and top cooling means 14, whereby the liquid condensateis fractionated and finished Astabilized end point gasoline may be ci@ by tray 26 and charged to the and pass out of the evaporator through line 32 withdrawn throughline 15 from the bottom of and temperature in stabilizer 12 being suitably -regulated to this end. Although I have stated that nished stabilized 'gasoline is withdrawn from separator 12, such gasoline ordinarily referably containing 'a considerable 'proportion of .thetotal butane and butylene present in the cracked products. for reasons which will later ,appear I may also operate/stabilizer 12 so as to send most of the butane and butylene overhead through 1ine.16, in which case the gasoline withdrawn through line 15 will be deficient in volatile The overhead vapors leaving stabilizer 12 through vline 16 are ordinarily introduced through valve 11 into fractionator 18 which is provided withuitable bottom heating means 13 70 and top vcooling means 88 whereby a fraction comprising predominatingly ethane and ethylene is removed in a vaporous or gaseousform from the top tliereoiL throughV line 8l while a. condenf sate consisting predominatingly of propaneV and propylene. together with any butane and butylene present, is withdrawn from the bottom thereof through line 82.

In .the operation of the aforedescribed cracking and fractionation system, I will ordinarily maintain a pressure of 100 to '150 lbs. per sq. in.

on reaction drum 40 while evaporator 23 and bubble tower I4 will ordinarily be operated under about 200 lbs. per sq'. in. pressure, which pressure will ordinarily be continued without reduction through the clay towers 5| and 51 and the separator 68., Stabilizer 12 and fractionator 18 will ordinarily be operated at pressures of approximately 100-350 lbs. per sq. in. and condensing and pumping means not shownmay be introduced in line 16 if it is desired to operate fracout of the system for refilling without Ashutting down the operation. The dried materials are then passed' through line 90 and optionally through heatm' or heat interchanger 9| into the catalytic polymerization chamber 92 which is ordinarily provided with internal cooling means 93. I have illustrated a chamber containing 4a mass of catalyst with internal cooling means but I may also use other arrangements and, for example, I may position my catalyst in tubes which are surrounded by the cooling medium and I may also maintain my catalyst in molten liquid form without the use of any support or carrier and bubble my gase's therethrough.

As catalyst I prefer'to use substances of the l.

aluminum halide stable double salt type wherein the other metallic halide may be sodium chloride, lithium chloride, sodium bromide,

cuprous chloride, antimony bromide, mercurio` bromide, etc., the compound sodium chloroaluminate being a tpyical example of this type ,my invention except that I prefer to use 4a catalyst of the above described type having a selective action on the heavier gaseous 'olens The catalyst reaction chamber 82 is preferably operated under pressures of 200 to 1000 lbs. per sq. in. and at temperatures of ZON-550 F. and the gas mixture is charged thereto at a rate equal to G-8000 cubic feet of free gas (i. e.,

measured at atmospheric pressure and 60 F.)

top outlet valve |00. In this case the gasoline and gas oil formed by the catalytic polymerization, together with any heavy or tarry materials, are passed through line |0| back to the previously described cracking system vand are either introduced through valve |02 into bubble tower I4 or through valve |03 `into evaporator 23. The latter arrangement willbe used if the products contain any substantial quantity of materials heavier than gas oil. Pumping means may belprovided in line |0| if'necessary. By this means `the gasoline produced by the catalytic polymerization is fractionated and sta-V bilized in the afore-described fractionating steps of the cracking system and is recovered and removed from the system through the line 15 v in admixture with the gasoline formed by cracking. Furthermore, any materials heavier than gasoline which are formed by the catalyticpolymerization are ultimately returned to the cracking furnace 31 for conversion into additional amounts of gasoline.'

The unconverted gases removed from fractionator 96 through valve |00 may be removed from the system through valve |04 for suitable outside treatment or disposal but may also be passed through valve |05 in line |06 to a. frac- Ationating system which is operated conjunc- -tion with the previously described oil cracking per cubic ft. of free catalyst volume per hour.

Reaction products removed from chamber 92 pass through valve 94 and line 85 into frac-v tlonator 86 which is provided with 4suitable bottom heating vmeans 91 (and top cooling means 98 and is operated under pressure of 50 to 350 pounds per sq. inch. I may operate fractionator 86 so asto remove' all liquid hydrocarbonsfcomsystem for the rectification of the gases and llight virgin naphtha flashed from the `crude oil in section |2 of the iiash tower. This fractionating system may be described as follows:

Vapors from section tower, being removed through line |1a, are cooled by condenser |01 and passed to separatorv |08 from the top of which, through `line |00, dry gas consisting essentially of methane is removed. The light `virgin naphtha lis removed from the bottom of the separator |08 by pump |09a and is passed through line V| |0 to stabilizer which is provided with suitable bottom heating means 2 and top cooling means ||3. From the bottom of stabilizer the stabilized light4 virgin naphtha from the crude is withdrawn through outlet valve I4, and gas consisting predominatingly of propanel and ethane, .together (under certain conditions) with some butane, is removed through line ||5 and may be removed from the system for suitable outside `treatment or disposal through valve I6 but is preferably passed through valve ||1 in line I|8 to fractionator I |9 which is provided with suitable bottom heating means |20 and top cooling means |2| whereby butaneis removed as a liquid bottom product through outlet |22 ,and propane, together' with any ethane present, is removed as a gaseous top product and may be eliminated from the system through valve |23 for suitable outside disposal or may be passed ,through valve |24- in line |25 to the gas cracking furnace |26 which will be later described in more detail.

Returning to the fractionator 96, the un',` l

I2 of the crude flash.

converted and essentially saturated gases re"- moved through outlet |00 may be passed through line |06 into the just. described light virgin naphtha stabilizing system, being paissed either through valve |21 and line |28 to the inlet of pump |09a or being passed through valve |29 and pump |30 directly into the fractionator I9. By this means all saturated gases, i. e., ethane,

I propane and butane, are recoveredin admixture prising gasoline and .heavier through the bot tom` outlet valve 88, removing all unconverted gases, including butane andlighter, through the Instead of passing gases and vapors from frac- Il -Therein it is subjected to non-catalytic polymer- Aethan'e may be removed through line |31 and may be eliminated from the system for suitable outside disposal through valve |38 or may be passed y through valve |39 to line |06 for treatment as previously described in stabilizer and/or fractionator I I9) or may be passed directly to gas cracking furnace |26 through valve |39a in line |39b.

I may also operate fractionators 96 and |33 mdersuch conditions that'only gas oil is obtained as a bottom product from fractionator 96, gasoline vapors passing overhead and being recovered as a bottom roduct from fractionator |33. The gas oil fry fractionatorg will be vreturned throug line |0| to evaporator 23 or bubble tower I In this -case the top product from fractionator |33 will contain all excess butane and lighter gases and I may pass this overhead product through valve |40 in line |4| into fractionator `|42 which is provided with suitable bottom heating means |43 and top cooling means |44 whereby excess butane is removed as a bottom product and withdrawn from the system for suitable disposal through outlet valve |45 in line |46, while propane together with any ethane is removed as vapor through outlet |41 and may be through valve |40 or may be passed through line |49 and valve |50 toline |06 to stabilizer and/orfractionator ||9 or to gas cracking furnace |26 directly, as previously described.

As was, vstated in connection with the description of fractionator 18, the gas fraction removed therefromA through line 6|`, containing ethylene as its predominant clef-ln constituent, is passed to the intake of pump |5| 'whereby it is passed to the high pressure-polymerization f ace |52.

, ization at pressures of 1000 to 3000 pounds per square inch and temperatures of 850 to ll00 F. I have illustrated the furnace |52 as being provided with a soaking coil type of iiow but instead of this, or in addition to this, I may utilizev an unheated reaction drum (not shown) follow,- ing the furnace. Products from the high pressure polymerization furnace |52 are passed 051 vthrough water-cooled condenser |53 or equivalent cooling means following which the pressure is reduced by valve |54 and 'the lliquid products and unconverted gases are passed to separator |55 wherein the pressure and temperature are such that a dry gas containing predominatingly.

methane and hydrogen'is removedfrom 'the top through offtake' |56, liquid products and condensed heavy gases being removdthrough bottomv offtake |,51. These liquid products and unand line |59 to ,line' |0| whereby they are returned to the evaporator 23 or bubble tower' I4 of 'the cracking system. Ordinarily, I prefer to fractionate unconverted gases separately and 4to 70 returnonly the liquid polymerization products n to the crackingV system. To this end I pass products from the bottom cf4 separator |55 through line |60 and valve I6||to fractionator |62 which is provided with suitable bottom heating means 'u |63 and top cooling4 means |64, gasoline, gas

eliminated from the system for suitable disposal.

converted gases may be passed through valve |58 Aoil and any heavier constituents of thehigh pressure polymerization products being withdrawn through line and valve |66 to line |0| whereby they are returned to evaporator 23 or bubble tower |4y and the gasoline is recovered in admixture with the cracked gasoline, While the liquid polymerization products heavier than gasoline are-subjected to cracking to obtain additional amounts of gasoline.

Gaseous products removed from the top of fractionator |62 through line |61 will consist mainly 5of ethane, propane, and butane, together with small amount of the corresponding oleins which have not been polymerized in furnace |52. I may eliminate these gases from the system through valve |68 or I may pass them through line |69 and valve |69a to the 'inlet of gas cracking furnace |26 which will be later described in more detail. I may-also pass them through line |10, valve |1| and valve |12 in line |13 to line |14 whereby they are passed to the inlet of pump 83 which charges the catalytic polymerization reaction chamber and whereby any propylene or butylenel contained therein will be catalytically polymerized while' other gaseous constituents will be givensuitable ultimate disposition by the previously described fractionating apparatus fol- I may also pass gases from fractionator |62 through line |10, valve |1| and valve |15 (using pumping means, not shown, if ne essary) to fractionator |16 which is provided th suitable bottom heating means |11 andgsuitable top 'cooling means |18 and whereby these gases will beV separated and ethane, together with y ethylene, will be withdrawn from the top hrough line |19 while any propane and butane, together with any propylene and butylene, will be withdrawn as a liquid condensate through offtake |60 (or I may eliminate ethane-propane through line |19 and withdraw butane through line |80), and optionally eliminated from the system through lto line |69 and thereby to the gas cracking fur' nace |26 later described in detail. -f I recycle part of this fraction through valve |84 to the high pressure polymerization furnace |52 it will be necessary to pass another part thereof through valve |65 to the gas cracking furnace 26. or to eliminate a part thereof from the system through valve |83', in order to prevent a gradual building up of ethane in the feed tothe high pressure polymerizationl furnace l|52. The balance between these possibilities will be determined mainly by the ethylene content of the unconverted gas from high pressure polymerization furnace |52 and the higher this ethylene content the larger the proportion of gas which I will ordinarily recycle to the furnace |52./

Although I do not limit myself thereto,I as an added element of lmy process I-prefer to operate my process in conjunctionwith a gas cracking step, referene having previously .beennade to 'l5 tionator. |33 (via outlet |31, valve |39, valve |05. I

rand a proylenic liquid fraction which is withgas cracking furnace |26 wherein this step is carried out. This furnace is operated at pressures of 0-100 pounds per square inch above atmospheric and temperatures of 1350-1650? F. The gas charged to the furnace is predominatingly saturated in character and ordinarily I prefer not to introduce any gas streams containing a large or predominating proportion of methane since methane does not yield readily to crackingv to form olefinic hydrocarbons. Furthermore, I prefer not to charge any substantial proportion of butane to furnace |26 since the amount of butane produced in my system can ordinarily be blended in toto in the finished gasoline and there fs therefore no advantage in subjecting it to cracking to form olenes for repolymrization to gasoline., I therefore prefer to charge gas crackingl furnacel |26 with a mixture consisting predominatingly of ethane and propane which may be obtained fram fractionator ||9 (by line |25), from fractionator |62 (Via offtake |61, valve |69a and line |69), from fracline |06, valve |29, valve |39a, and through line |39b), from fra/ctionator |42 (via outlet |41, line |49, valve |50, line |06, valve |05, valve |3911, and through line |3912) or from fractionator |16 (via offtake |19, valve and lines |86 and |69).

It will also be seenv that, as previously described,

the gas from fractionator ||9 may contain saturated unconverted gases from catalytic polymerization chamber 92 which are eliminated in yfractionators 96, |33 and/or |42 and 'are conveyedy to fractionator ||9 through line |06 (or via line |06, Valve |21, line |28, separator |08 and stabilizer III). By these various arrangements I preferably charge gas cracking furnace |26 with all ethane and propane produced in my A indirect cooling means, following which the cooled gases are introduced into tar separator |88 wherein tar is removed from the-system through oftake |89 and gases containing a large proportion of gaseous oleiines, predominatingly.

ethylene, are removed through line |90 for treatment by high pressure polymerization in furnace |52. I prefer to separate inert gases, such as methane and hydrogen, from .this gas prior to introduction into furnace |52 and may do so by any convenient means but preferably I introduce said gases by pump |9| and line |92 into separator 68 wherein it joins gases and liquid products from the cracking system whereby its methane and hydrogen content are eliminated in conjunction with methane and hydrogen from the cracking system, and the ethylene formed in gas crac g furnace |26 thus ultimately passes to hi pressure polymerization furnace |52 vialine 8| in conjunction with similar ethylenic gases produced in the cracking system. C, I have previously stated that I prefer to operatstabilizer 12 so that overhead gases, consistingpredominatingly of ethane, ethylene, propane and propylene, are passedinto fractionatpr 18 and are therein separated into an ethylenlc gaseous fraction which is charged through'linc 8| fohigh pressure polymerization furnace |62,

. gaseous oleflnes are polymerized to liquids in the catalytic polymerization chamber 92 while the ethylene present in the feed gas is converted to a minor degree only-` In this case I may operate the fractionating system following the catalytic reaction chamber 92, as exemplified by fractionators 96, |33 and |42, so-as to separate an ethylenic gas fraction which will contain higher boiling gases and which is passed directly to the inlet of pump |5`| supplying the high pressure polymerization furnace |52, either from fractionator |33 through oitake |31 and valved line |95, or from fractionator |42 through offtake |41, and valved line |96.

As previously stated, I prefer to operatey my improved process using the catalytic polymerization step, the high pressure non-catalytic polymerization step and the gas cracking step, all in conjunction withan oil cracking step as previously described. I may, however, operate only the catalytic polymerization step or the catalyticv polymerization step plus the high pressure non-catalytic polymerization step, in coneliminate butylene from this gasoline wherebyI may increase its butane content and thereby improve its volatility and starting characteristics without increasing its vapor-locking tendency in internal combustion engine systems; that my gasoline has improved antiknock value; and that I accomplish these results with a minimum of apparatus and a maximum of economy of fuel and other operating costs. This application is a division of my copending appcation serial No. 757,902, med December 17, 1934. (Patent No. 2,160,286, granted May `30, 1939.) i y i It will be understood that I am not limiten in my invention as above described except as set forth in the claims as follows.

I claim:

1.' In the process of converting an admxture of normally gaseous hydrocarbons into normally liquid'hydrocarbons; the steps comprising subjecting an admixture of normally gaseous hy-y drocarbons to thermal polymerization to convert a part of the hydrocarbons into normally liquid hydrocarbons; fractionating the products from 6G` the thermal polymerization step to obtain as separate fractions, normally liquid hydrocarjunction -with my oil cracking step as will be i bons, a fraction of normally gaseous hydrocarbons containing C2 hydrocarbons as thepredominating hydrocarbon constituent, and a fraction of normally gaseous hydrocarbons containing into normally liquid hydrocarbons; fractionating theproducts from the catalytic polymerization step to obtain as separate fractions, norh Y i mally liquid hydrocarbons, and unconverted normally gaseous hydrocarbons; and passing said fractionv of unconverted normally gaseous hydrocarbons Iand the fraction of normally gaseous hydrocarbons containing C2 hydrocarbons as thepredominating hydrocarbon constituent .to the thermal polymerization step for further processing. v

2. In the process of converting an admixture of normally'gaseous hydrocarbons into normally liquid hydrocarbonsboiling within the gasoline range; the steps comprising subjecting an admixture of normally gaseous hydrocarbons to thermal polymerization at elevated temperatures and pressures sumcient to `convert a portion of the gases into normally liquid hydrocarbonsi boiling within the gasoline range; fractionating the products fromthe ltherm-al polymerization step to obtain as separate fractions, normally liquid hydrocarbons, a fraction of normally gaseous hydrocarbons containing C2 hydrocarbons as the predominating hydrocarbon constituent, and a fraction of normally gaseous olefin-containing hydrocarbons containing Cz and C4 hydrocarbons as the predominating hydrocarbonl constituents; subjecting said fraction of normally gaseous olen-containing hydrocarbons to catalytic polymerization atJ elevated pressures and temperatures lower than those employed in bons -a fraction of'normally liquid hydrocarbons boiling within the gasoline range. f

3. In the process of converting an admixture of normally gaseous hydrocarbons into normally liquid hydrocarbons; the steps comprising jsub-, jecting an admixture of normally gaseous hy. drocarbons 4to thermal polymerization :at pressure within the range of 1000-3000 pounds per squareinch and temperatures within the range Afao of 850-1100 F. to convert apart oi the hydrocarbons into normally liquid hydrocarbons; removing the bulk of the hydrogen and methane from the products of the thermal polymerization step and fractionatingl the remaining products to obtain as separate fractions, normally lliquid hydrocarbons, a fraction lof normally gaseous hydrocarbons containing Ca hydrocarbons `as the predominating hydrocarbon constituent and .a fraction of normally gaseous oleiln-containing hydrocarbons containing Ca and C4 hydrocarbons as the predominating hydrocarbon constituents; subjecting said fraction of nor- 5 mally .gaseous olefin-containing hydrocarbons normally gaseous hydrocarbons and the fraction of normally gaseous hydrocarbons lcontaining C2 hydrocarbons as the predominating hydrocarbon constituent to the thermal polymerization step for further processing. p

4. In the/process of converting an admixture of normally gaseous hydrocarbons into normally liquid hydrocarbons; the steps comprising subjecting an admixture of normally gaseous hydrocarbons to thermal polymerization at elevated temperatures and pressures sutlicient to convert a part of the hydrocarbons into normallyliquid hydrocarbons; removing the bulk of the hydrogen and methane from the products of the thermal polymerization step and fractionating the remaining products to obtain as separate fractions,4 normally liquid hydrocarbons, a fraction of normally gaseous hydrocarbons containing C2 hydrocarbons as the predominating hydrocarbon constituent and a fraction of normally gaseous olen-containing hydrocarbons containing Ca and C4 hydrocarbons as the predominating hydrocarbon constituents; subjecting said fraction of normally gaseous olefin-containing hydrocarbons to catalytic polymerization to convert a part of the hydrocarbons into normally liquid hydrocarbons; fractionating. the products from the catalytic olymerization step to obtain as separate fracions, normally liquid hydrocarbons, and unconvertedv normally gaseous hydrocarbons; passing said fraction of unconverted normally gaseous hydrocarbons and the fraction of normally gaseous hydrocarbonscontaining Cz hydrocarbons as the predominating hydrocarbon constituent to the thermal polymerization step for further polymerization and recovering normally liquidhydrocarbons. a

5. -In the process of converting an admixture of normally gaseous hydrocarbons into v normally liquid hydrocarbons; the steps comprising` subjecting an admixture of normally gaseous hydrocarbons to thermal polymerization 'at elevated temperatures and pressures suiiicient to convert a part of the hydrocarbons into normally liquid hydrocarbons; fractionating the products from the thermal polymerization step to obtain as separate fractions, normally liquid hydrocarbons, a fraction of normally gaseous hydrocarbons containing Cz hydrocarbons as the predominating hydrocarbonconstituent, and a fraction of normally gaseous olefin-containing hydrocarbons containing Caand C4 hydrocarbons as the predominating hydrocarbon constituents; subjecting said fraction of normally gaseous olefin-containing hydrocarbonsto catalytic conversion at an elevated pressure and a temperature within the range of Z50-550 F. to convert a part ofthe hydrocarbons into normally liquid hydrocarbons; fractionating the products from the catalytic conversion step to obtain as separate fractions, normally liquid hydrocarbons and unconverted normally gaseous hydrocarbons; passing said fraction of unconverted normally gaseous hydrocarbons and, the fraction of normally gaseous hydrocarbons containing C2 hydrocarbons as the predominating hydrocarbon constituent to the thermal polymerization step for further polymerization; and recovering normally liquid hydrocarbons from the system.

6. In the process of converting an admixture of normally gaseous hydrocarbons into normally 'liquid hydrocarbons; the steps comprising subjecting an admixture of,` normally gaseous hydrotemperatures and pressuressuiiicient to convert-'a part of the hydrocarbons into normally liquid hycarbons ,to 'thermal polymerization at elevated drocarbons: separating hydrogenY and methane from the products of the thermal polymerization step and fractionating the remaining products to obtain as separate fractions, normally liquid hydrocarbons, a fraction of normally gaseous hydrocarbons containing C2 hydrocarbons as the predominating hydrocarbon constituent, and a iraction of normally gaseous olefin-containing hydrocarbons containing Cs and C4 hydrocarbons. as the predominating hydrocarbon constituents; subjecting said fraction of normally gaseous olefincontaining hydrocarbons containing C: and 'C4 hydrocarbons as the predominating hydrocarbon constituents to catalytic polymerization to convert a part oi' the hydrocarbons into normally liquid hydrocarbons; fractionating the products from the catalytic polymerizationstep to obtain as separate fractions, normally liquid hydrocarbons, and an unconverted fraction of normally gaseous hydrocarbons; passing a part of said fraction of unconverted normally gaseous hydrocarbons and the fraction o! normally gaseous hydrocarbons containing Cz hydrocarbons as the predominating hydrocarbon constituentl to the. thermal polymerization step for further processing; and recovering normally liquid hydrocarbons from the system.

'1. In the process of converting an admixture of normally gaseous hydrocarbons into normally 3) liquid hydrocarbons; the steps comprising subiecting an admixture of normally gaseous hydrocarbons to thermal polymerization at elevated temperatures and pressures sumcient to convert a part of the hydrocarbons into normally liquid hydrocarbons; separating hydrogen and methane from the products oi' the thermal polymerization step and fractionating the remaining products to obtain as separate fractions, normally liquid hydrocarbons, a fraction of normally gaseous hydrol l carbons containing C2 hydrocarbons as the predominating hydrocarbon constituent, anda fraction of normally gaseous olen-containing hydrocarbons containing Ca and C4 hydrocarbons as the predominating hydrocarbon constituents; subjecting said fraction of normally gaseous olefincontaining hydrocarbons containing Ca and Ct hydrocarbons as the predominating hydrocarbon constituents to catalytic polymerization to con- 'vert a part of the, hydrocarbons into normally ROBERT F. 

